CN109647520A - Catalyst for polyoxymethylene dimethyl ether preparation - Google Patents
Catalyst for polyoxymethylene dimethyl ether preparation Download PDFInfo
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- CN109647520A CN109647520A CN201710941272.5A CN201710941272A CN109647520A CN 109647520 A CN109647520 A CN 109647520A CN 201710941272 A CN201710941272 A CN 201710941272A CN 109647520 A CN109647520 A CN 109647520A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the catalyst prepared for polyoxymethylene dimethyl ether, mainly solve the problems, such as the prior art using methanol, dimethoxym ethane and paraformaldehyde as that there are catalyst activities in reaction raw materials synthesizing polyoxymethylene dimethyl ether technique is low, selectivity is low, by using the catalyst prepared for polyoxymethylene dimethyl ether, the catalyst is metal ion-modified cation exchange resin, the metal includes the technical solution of group VIII metal, be can be used in the industrial production of polyoxymethylene dimethyl ether.
Description
Technical field
The present invention relates to the catalyst prepared for polyoxymethylene dimethyl ether.
Background technique
In recent years, as the industrial revolution influences the resource grid goed deep into increasingly and China is distinctive " more coals, have gas at few oil "
Office, China's oil resource growing tension, petroleum supply pressure unprecedentedly increase.It is expected that 10~20 years following, China's oil supply rate
Only~50%.How to be become using the energy crisis that China's coal resources abundant solve China and is badly in need of solving for researcher
Certainly the problem of.Therefore the attention that novel oil product substitute is increasingly subject to people is developed by coal-based methanol.
Dimethyl ether is proposed as a kind of procetane earliest, however since its own cold starting performance is poor, room temperature
Lower vapour pressure is high, is easy to produce vapour lock makes dimethyl ether significantly raised as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether,
That is Polyoxymethylene dimethyl ethers (PODE), is the common name of a substance, and skeleton symbol can be expressed as
CH3O(CH2O)nCH3, octane number (> 30) with higher and oxygen content (42~51%).When the value of n is 2~10, object
Rationality matter, combustibility and diesel oil are very close, preferably resolve dimethyl ether and lack as existing for derv fuel blend component
It falls into.Therefore polyoxymethylene dimethyl ether can be used as novel cleaning diesel component, and the additive amount in diesel oil, can up to 30% (v/v)
To improve the combustion position of diesel oil within the engine, the thermal efficiency is improved, reduces particulate matter and CO in tail gasxAnd NOxRow
It puts.It is reported that the CH of addition 5~30%3OCH2OCH3NO can be reducedxDischarging 7~10%, PM reduces by 5~35%.By coal Ji Jia
Alcohol synthesis PODE can not only replace part diesel oil, moreover it is possible to improve the efficiency of combustion of diesel oil, reduce diesel combustion to the danger of environment
Evil has important strategic importance and good economic value.
CN 101048357A (method for preparing polyoxymethylene dimethyl ether) is described using inorganic acid, sulfonic acid, heteropoly acid, acid
Property ion exchange resin, zeolite, aluminium oxide etc. be used as catalyst, be reactant synthesizing polyoxymethylene by dimethoxym ethane and metaformaldehyde
The method of dimethyl ether.But using the conversion ratio of existing catalyst and selectivity all up for improving.
Cation exchange resin is shown good as solid acid catalyst in the esterification of Aquo System, etherification reaction
Catalytic perfomance, but its acid strength is lower.It generallys use and prepares support type resin, make activity by increasing acidity of catalyst
It is improved.Metal-modified resin can be used, new acid site is formed on a catalyst, can't be handed over by other metal ions
It changes, which solves in the case where catalyst keeps high activity in industrial application for polyoxymethylene dimethyl ether synthesis and it is acid not
The problem of meeting metal ion contained in raw material replaces and inactivates.
Summary of the invention
The first technical problem to be solved by the present invention is that the prior art is former for reaction with methanol, dimethoxym ethane and paraformaldehyde
There is a problem of that n=2-10 selectivity of product is low in material synthesizing polyoxymethylene dimethyl ether technique, provides a kind of new for polyformaldehyde
The standby catalyst of dimethyl ether.The catalyst has the advantages that the selectivity of product of n=2-10 is high.
The second technical problem to be solved by the present invention is to provide a kind of using catalyst described in one of above-mentioned technical problem
Preparation method.
The third technical problem to be solved by the present invention is the application of catalyst described in one of above-mentioned technical problem.
One of in order to solve the above-mentioned technical problem, technical scheme is as follows:
For the catalyst of polyoxymethylene dimethyl ether preparation, the catalyst is metal ion-modified cation exchange tree
Rouge, the metal include group VIII metal.
It further include the metal include IIIA metal in above-mentioned technical proposal.
In above-mentioned technical proposal, the Group IIIA metal is preferably Ga.Ga and VIII group element improve to n=2~
There is synergistic effect in terms of the selectivity of 10 PODE.Ratio between Ga and VIII group element is not particularly limited, as long as Ga
Comparable synergy can be obtained in catalyst by existing simultaneously with VIII group element.
As non-restrictive, the mass ratio of Ga and VIII group element is 0.01~100, further non-within this range
Limited citing such as 0.1,0.5,0.8,1,1.5,2,3,4,5,6,7,8,9,10 etc..
In above-mentioned technical proposal, the VIII group element is selected from least one of Fe, Co and Ni.
In above-mentioned technical proposal, the more preferable modified metal includes at least two and Ga in Fe, Co and Ni, this
When above two VIII element between there is synergistic effect in terms of improving to the selectivity of the PODE of n=2~10.At this point, Ni,
Ratio between Co and Fe is not particularly limited, as long as at least two in Ni, Co and Fe exist simultaneously the equal energy in catalyst
Comparable synergy is obtained, between such as, but not limited to Co and Ni, between Ni and Fe.
As non-restrictive, between above two VIII element, such as between Co and Ni, the mass ratio of Ni and Fe be
0.01~100, within this range further non-restrictive such as 0.1,0.5,0.8,1,1.5,2,3,4,5,6,7,8,9,
10 etc..
As most preferred technical solution, the modified metal includes simultaneously Fe, Co, Ni and Ga, at this time to n=2~10
The selectivity of PODE reach best.
In above-mentioned technical proposal, the content of modified metal is not particularly limited in catalyst, such as, but not limited to catalyst
The content of middle modified metal is greater than 0 and to be less than or equal to 9.8w%.
In above-mentioned technical proposal, the full exchange capacity of the resin is preferably 3.0~5.9mmol/g.
In above-mentioned technical proposal, the resin can be gel-type or macroporous type.
In order to solve the above-mentioned technical problem two, technical scheme is as follows:
The preparation method of catalyst described in any one of technical solution of one of above-mentioned technical problem, is included in catalyst
In the presence of the acid of amount, by the sulfonic acid polystyrene cation exchange resin and the suspension containing the modified metal-oxide
Contact carries out ion exchange.
In above-mentioned technical proposal, the acid is not particularly limited, as long as can react with containing the modified metal-oxide
Obtained salt can be dissolved in solvent used in the suspension and be ok, under this principle be such as, but not limited to hydrochloric acid, nitric acid or
At least one of carboxylic acid of C2~C10.
In above-mentioned technical proposal, the carboxylic acid can be hydroxyl substituted carboxylic acid, such as, but not limited to hydroxyacetic acid, lactic acid,
Tartaric acid, citric acid etc..
In above-mentioned technical proposal, the carboxylic acid can be the monoacid of C2~C10, such as, but not limited to acetic acid etc..
To solve above-mentioned technical problem three, technical solution of the present invention is as follows:
Catalyst is in synthesizing polyoxymethylene dimethyl ethers described in any one of technical solution of one of above-mentioned technical problem
Using.
The synthetic method of polyoxymethylene dimethyl ethers for example can be, using methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein
Methanol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0~10): (0~10): 1, the dosage of methanol and dimethoxym ethane cannot be simultaneously
0, raw material is contacted with catalyst described above, and reaction generates polyoxymethylene dimethyl ether.
In above-mentioned technical proposal, catalyst amount is preferably the 0.05~10% of raw material weight；More preferably raw material weight
0.1~5%.
In above-mentioned technical proposal, reaction temperature is preferably 70~200 DEG C.
In above-mentioned technical proposal, reaction pressure is preferably 0.2~6MPa.
In above-mentioned technical proposal, the reaction time is preferably 1 to 20 hour, and more 4 to 12 hours.
In above-mentioned technical proposal, the sum of dosage of methanol and dimethoxym ethane and the mass ratio of paraformaldehyde are preferably in raw material
(0.4~5): 1；Methanol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0.2~10): (0.5~10): 1.
In the case where the composition of catalyst of the present invention is clear, the preparation of catalyst is not particularly limited, Ke Yican
Ion-exchange process commonly used in the prior art is examined to be prepared.It such as may include following steps: by sulfonic acid sodium form polystyrene
Cation exchange resin is washed with deionized water to outflow clear water, impregnates 1 with 0.5~20% strong acid (such as hydrochloric acid or sulfuric acid)
~12h impregnates 1~12h with deionized water or alcohol solution dipping, is washed with deionized later to pH=6 to get this hair is arrived
The bright sulfonic acid polystyrene cation exchange resin.When sulfonic acid type of the present invention can also be directly obtained from commercially available channel
Polystyrol cation exchange resin, rather than sulfonic acid sodium form, may be used to the preparation of catalyst of the present invention.
Using catalyst of the invention, the PODE yield of n=2~10 is good, and the selectivity of product of n=2~10 is up to 88.3%,
Achieve preferable technical effect.
Heretofore described full exchange capacity is in terms of butt resin.
Below by embodiment, the present invention is further elaborated, the raw material paraformaldehyde used in embodiment and comparative example
The degree of polymerization be 5, selectivity of product on the basis of paraformaldehyde by target of the polyoxymethylene dimethyl ether that the degree of polymerization is 2~10 produce
Object calculates.
Specific embodiment
[embodiment 1]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
The Ga (OH) that acid type polystyrene cation exchange resin and 300ml are 2 grams containing Ga31 drop ice vinegar is added in aqueous suspension mixing
Acid, mixing stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtain the catalyst that Ga content is 2w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 2]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin, the Ni (OH) for being 2 grams containing Ni with 300ml under nitrogen protection2Aqueous suspension mixing, adds
Enter 1 drop glacial acetic acid, mix, stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtaining Ni content is 2w%'s
Catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 3]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin, the Co (OH) for being 2 grams containing Co with 300ml under nitrogen protection2Aqueous suspension mixing, adds
Enter 1 drop glacial acetic acid, mix, stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtaining Co content is 2w%'s
Catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 4]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin, the Fe (OH) for being 2 grams containing Fe with 300ml under nitrogen protection2Aqueous suspension mixing, adds
Enter 1 drop glacial acetic acid, mix, stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtaining Fe content is 2w%'s
Catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 5]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin, with 300ml containing the Ga (OH) that Ga is 1 gram and Ni is 1 gram under nitrogen protection3And Ni
(OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, dry extremely in vacuum oven
Constant weight, obtaining Ga content is the catalyst that 1w% and Ni content is 1w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 6]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin, with 300ml containing the Ga (OH) that Ga is 1 gram and Co is 1 gram under nitrogen protection3And Co
(OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, dry extremely in vacuum oven
Constant weight, obtaining Ga content is the catalyst that 1w% and Co content is 1w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 7]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin, with 300ml containing the Ga (OH) that Ga is 1 gram and Fe is 1 gram under nitrogen protection3And Fe
(OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, dry extremely in vacuum oven
Constant weight, obtaining Ga content is the catalyst that 1w% and Fe content is 1w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 8]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Co is 0.5 gram and Ni is 0.5 gram
Ga(OH)3、Co(OH)2With Ni (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature,
Dry to constant weight in vacuum oven, it be 0.5w% and Ni content is urging for 0.5w% that obtain Ga content, which be 1w%, Co content,
Agent.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 9]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Co is 0.5 gram and Fe is 0.5 gram
Ga(OH)3、Co(OH)2With Fe (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature,
Dry to constant weight in vacuum oven, it be 0.5w% and Fe content is urging for 0.5w% that obtain Ga content, which be 1w%, Co content,
Agent.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 10]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Ni is 0.5 gram and Fe is 0.5 gram
Ga(OH)3、Ni(OH)2With Fe (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature,
Dry to constant weight in vacuum oven, it be 0.5w% and Fe content is urging for 0.5w% that obtain Ga content, which be 1w%, Ni content,
Agent.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 11]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Co is 0.4 gram, Ni is 0.3 gram and Fe
For 0.3 gram of Ga (OH)3、Co(OH)2、Ni(OH)2With Fe (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixes,
24 hours are stood at room temperature, dry to constant weight in vacuum oven, it is 0.4w%, Ni that obtain Ga content, which be 1w%, Co content,
Content is the catalyst that 0.3w% and Fe content is 0.3w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and
4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 12]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Co is 0.4 gram, Ni is 0.3 gram and Fe
For 0.3 gram of Ga (OH)3、Co(OH)2、Ni(OH)2With Fe (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixes,
24 hours are stood at room temperature, dry to constant weight in vacuum oven, it is 0.4w%, Ni that obtain Ga content, which be 1w%, Co content,
Content is the catalyst that 0.3w% and Fe content is 0.3w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 90 DEG C and
4h is reacted under 0.6MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product
Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[comparative example 1]
In proportion for embodiment 1, difference is only that the catalyst used is poly- for drying sulfonic acid type described in embodiment 1
2 grams of styrene cation exchange resin, other process conditions are same as Example 1, the results are shown in Table 1.
Table 1
N is the degree of polymerization, product CH3O(CH2O)nCH3。
Claims (10)
1. for the catalyst of polyoxymethylene dimethyl ether preparation, the catalyst is metal ion-modified cation exchange resin,
The metal includes group VIII metal.
2. catalyst according to claim 1, it is characterized in that the VIII group element in Fe, Co and Ni at least one
Kind.
3. catalyst according to claim 1, it is characterized in that the content of modified metal is greater than 0 and to be less than etc. in catalyst
In 9.8w%.
4. catalyst according to claim 1, it is characterized in that the full exchange capacity of the resin is 3.0~5.9mmol/g.
5. catalyst according to claim 1, it is characterized in that the resin is gel-type or macroporous type.
6. catalyst according to claim 1, it is characterized in that the resin sulfonic acid polystyrene cation exchange resin.
7. catalyst according to claim 6, it is characterized in that sulfonic acid polystyrene cation described in the resin exchanges
Resin includes crosslinked polystyrene skeleton and sulfonic acid group；
8. the preparation method of catalyst according to any one of claims 1 to 7, including inciting somebody to action in the presence of the acid of catalytic amount
The sulfonic acid polystyrene cation exchange resin with contain the modified metal-oxide and/or the modified metal hydroxide
The suspension contact of object carries out ion exchange.
9. preparation method according to claim 8, it is characterized in that the acid is the carboxylic acid of hydrochloric acid, nitric acid or C2~C10
At least one of.
10. application of the catalyst according to any one of claims 1 to 7 in synthesizing polyoxymethylene dimethyl ethers.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1506444A (en) * | 2002-12-13 | 2004-06-23 | 中国石油天然气股份有限公司 | Catalytically cracking process of modifying gasoline |
| AU2010246340A1 (en) * | 2004-01-21 | 2010-12-09 | Chevron Phillips Chemical Company Lp | Dual metallocene catalyst for producing film resins with good machine direction (MD) Elmendorf tear strength |
| CN106582835A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether synthesis catalyst |
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2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1506444A (en) * | 2002-12-13 | 2004-06-23 | 中国石油天然气股份有限公司 | Catalytically cracking process of modifying gasoline |
| AU2010246340A1 (en) * | 2004-01-21 | 2010-12-09 | Chevron Phillips Chemical Company Lp | Dual metallocene catalyst for producing film resins with good machine direction (MD) Elmendorf tear strength |
| CN106582835A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether synthesis catalyst |
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